Process of manufacturing amino ketones



Patented June 25, 1940 PROCESS OF MANUFACTURING AMINO 'KETONEB HenryMartin and'ltudolt Hilt, Basel, Switzerland, assignors to the firm J. R.'Geigy A. G.,

Basel, Switzerland No Drawing. Application, July 12, 19a, Serial No.

218,879. "In Switzerland July 16, 193vv 6 Claims.

' This invention relates to the manufacture of amino ketones and hasfor. its object the production of amino ketones, having valuabletechnical properties, and being useful for various purposes.

According tothe present invention amino ketones are produced by causingcompounds of the type v n-cn-co-O-nim (with exchangeable halogen in' thebenzene nucleus) and wherein'R represents ahigher molecular, saturatedor unsaturated, substituted or 1 unsubstituted, aliphatic or alicyclicradical with more than 5 C-atoms, which may be linked by heteroatoms orheteroatom groups to the 4 a-benzyl palmitic acid, behenic acid,dcdecylis ample phenyl-acetic acids, phenylacetic group, and Xrepresents a hydrogen atom, alkyl,

aralkyl or aryl, to act uponsecondary amines, capable of reacting,substit d by like or unlike substituents at the nitrogen atom, ofaliphatic,

26 aliphatic araliphatic, aliphatic-hydroaromatic or heterocyclicnature. i

The resulting tertiary amino ketones may either be vfurther treated withthe usual alkylating agents or converted directly into salts of organicto or inorganic acids.

The halogen ketones used as initial material are produced, for example,by causing aliphatic or alicyclic earboxylic acids or their chlorides oresters to act upon aromatic halogenated hydroat carbons or theirsubstitution products.

As carboxylic acids there are mainly suitable higher molecular saturatedor-unsaturated, also substituted, carboxylic acids, such as oleic acid,stearic acid, paimitic acid, a-methyl palmitic acid, r

oxyacetic acid, campholic acid, fencholic acid, naphthenic acids.-

It is however also possible by means of suitable araliphaticcarbonylicacids (such as for exacid chlorides respectively) to obtain, by reactionwith aromatic halogenated hydrocarbons, halogen ireto'nes which can thenbe; converted, by alkylating with higher molecular, aliphatic oralicyclic '50 mineral acid esters-obtained for example from mineralacids and the alcohols which are produced byhydrogenating naturallyoccurring fats, oils, resins, naphthenic acids-Ante compoundsconstituted in the manner claimed; containing to reactive halogen(according to theprinciple oi 'coholates there can be obtained ketoneswith.

5 very often bodies capable of being easily distilled tives.

the compounds are also interesting.

(Cl. 260-457) I alkylation of the desoxybenzoins). Bytreatinga-4-dichloro-aceto-phenone or its 'alkyl derivatives substitutedin the aliphatic chain, with allphatic or alicyclic amines mercaptans oralhalogencapable of reacting, oi. which the all-'- phatic or alicyclicradical is linked by nitrogen,

sulphur or oxygen to the roup. i v The aromatic hydrocarbons which areused mainly consist of halogenated benzenes, .suchas chlorobenzene and.its homologues'.

The halogen ketones containing reactive halogen described, can beconverted by simple proc esses with secondary amines capable ofreacting, into the corresponding tertiary amino ketones. For thispurpose there are equally suitable 611- so methylamine, diethylamine,dibutylamine, di-

amylamine, methylben zylamine," methylcyclohexylamine, or piperidine inthe presence of certain catalysts such as for example copper powder.

' The tertiary amino iretones obtained by the all conversion withaminesmay subsequently be further aikylated, which is best effected by meansof the most usual alkylating agents, for example with methyl iodid'e orwith dialkyl sulphates such as dimethyl sulphate, diethyl' sulphate orwith it toluene sulphonic alkyl acid esters and halogenbenzene sulphonicacid alkyl esters. The N-containing compounds with the excep tion of thequaternary'compounds as bases are under reduced pressure, which aredimcultly soluble or insoluble in water. They can be converted intowater-soluble compounds by the methods generally usual for ammoniaderiva- With inorganic or organic acids there are formed salts,,forexample hydrochlorides, sulphates, phosphates, silica-fiuorates,for-mates, and citrates. g The amino ketones can be used. for the mostvarious purposes. They form valuable wetting, dispersing and emulsifyingagents, especially however softening agents for cotton and pre cipitatedcellulose, but also valuable agents for improving the fastness to wateroi direct dyeings or-stripping agents for naphthol-Asor vat=dyean Inpart they are also suitable forprotecting wool, 'feathers,furs,;hair,and leather from moths and other wool destroying insects. '.ihe

bactericidal and fungicidal, properties of some of r The invention isillustrated by the following examples. the parts being by weight wherenothing other is said:

Example 1 500 parts of chlorobenzene are treated with 100 parts ofaluminium chloride and whilst stirring 200 parts of stearic acidchloride are added in drops. After 15 hours at IO-80 C. cooling takesplace, the mixture is poured into water and distilled with steam untilall the excess of chlorobenzene has disappeared. There remain 250 partsof p-chlorostearophenone.

75 parts of this compound are heated to 220- 230 C. for 20 hours in anautoclave with an alcoholic solution of 22.5 parts of dimethylamine in500 volume parts of alcohol and some copper powder. After removing thecopper powder and.

expelling thesolvent there are obtained 67 parts ofp-dimethylamino-stearophenone.

58 parts of p-dirnethylamino-stearophenomand 31 parts of diethylsulphate are heated for 2 hours to 130-140? C. There are formed 89 partsof the water-solublep-dimethyl-ethyl-ammonium-stearophenone-etho-sulphate. v

The formulae on which this example is based are the following: v

Instead of stearic acid chloride other acid chlorides may be used, suchas palm nut fatty acid chloride, e-methyl palmitic acid chloride, oleicacid chloride or fencholic acid chloride. The dimethylaminemay also bereplaced by diethylamine, dipropylamine or methylcyclohexylamine. Byreplacing the diethyl sulphate by toluene sulphonic acid methyl-ester,there are obtained. substances with difierent properties.

Example 2 500 parts of chlorobenzene are treated with 300 parts ofaluminium chloride and there are added in drops, while stirring, 309parts of phenylacetic acid chloride. After heating for 2 hours at 50 C.the mixture is poured on ice, the exsoda lye and hydrochloric acid,-then dried and expelled. The residue is distilled, boiling point at 1.3m./m. 270-280 C. I p

45.4 parts of the p-chloro-ms-hexadecy11-desoxybenzoin are heated for 20hours to 220 C. in

a closed vessel with a solution of 20 parts of dimethylamine in 250volume parts of alcohol and some copper powder. The separated product issucked off, dissolved in benzene, the copper powder removed and thesolution again evaporated.

23 parts of p-dimethylamino-ms hexadecyldesoxybenzoin are heated with 7parts of dimethyl sulphate for 1-hour to 125 C. There is formed awax-like mass which is clearly soluble in water.

The formulae on whichthis example is based are the following:

iaHaa (CHi)tEN- -CO.CH- v lbACH: 1 15K Instead of thep-dimethylamino-ms-hexadecyldesoxybenzoin there may also beused thep-dimethylamino-ms-dodecyl-desoxybenzoin.

.What we claim is:

1. A process for the production of aromatic amino ketones, comprisingcausing a ketone of the formula wherein R represents a member of'thegroup. consisting of alkyl, cycloalk yl, allq l-Y-, cycloallgyl- Y-,containing more than 5 C-atoms with Y representing a member selectedfrom the group consisting of O, S, N-allwl and NT-cyclo alkyl. X

. represents a member of the group consisting-of H, alkyl, aralkyl andaryl, to react with a sec-- ondary amine, capable of reacting, selectedfrom thegroup consisting of aliphatic, aliphatic-araliphatic,aliphatic-hydroaromatic and heterocyclic nature.

2. A process for the production of aromatic quaternary amino ketones,comprising treating the p-aminoketones obtained by the process of claim1 with alkylatingagents.

3. A process for the production of aroinatic quaternary amino ketones,comprising causing a ketone of the formula R-C OO-halogen with R asaliphatic radical with at least 6 carbon atoms, to react with adialkylamide and treating the resulting p-dialkylamino ketone of theformula l alkyl G alkyl with a dialkyl sulphate.

4. A process for the production of an aromatic quaternary amino ketone,comprising causing p-chlorostearophenone to react with dimethylamine andreacting theresulting p-dimethylamino-stearophenone with dimethylsulphate.

5. A process for the production of an aromatic I quaternary aminoketone, comprlsing causing p-chlorostearophenone to reactwlth'dimethylamine and reacting the resultingp-dimethylamino-stearophenone with diethyl sulphate.

6. A process for the production of an aromatic quaternary amino ketone,comprising causing p-chloro-laurophenone (made from palm nut fatty acidchloride and p-chlorobenzene in the presence of A1012) to react withdimethylamine and reacting the resulting p-dimethylaminolaurophenonewith dimethyl sulphate.

' HENRY MARTIN.

RUDOLF HIRT.

